Thin-film solar cells and photodetectors having enhanced optical absorption and radiation tolerance

ABSTRACT

Subwavelength random and periodic microscopic structures are used to enhance light absorption and tolerance for ionizing radiation damage of thin film and photodetectors. Diffractive front surface microscopic structures scatter light into oblique propagating higher diffraction orders that are effectively trapped within the volume of the photovoltaic material. For subwavelength periodic microscopic structures etched through the majority of the material, enhanced absorption is due to waveguide effect perpendicular to the surface thereof. Enhanced radiation tolerance of the structures of the present invention is due to closely spaced, vertical sidewall junctions that capture a majority of deeply generated electron-hole pairs before they are lost to recombination. The separation of these vertical sidewall junctions is much smaller than the minority carrier diffusion lengths even after radiation-induced degradation. The effective light trapping of the structures of the invention compensates for the significant removal of photovoltaic material and substantially reduces the weight thereof for space applications.

RELATED CASES

The present patent application claims the benefit of Provisional PatentApplication Ser. No. 60/332,777 filed on Nov. 16, 2001 for “Method OfDeeply Etched Subwavelength Structures For Enhanced Optical AbsorptionIn Solar Cells And Photodetectors.”

STATEMENT REGARDING FEDERAL RIGHTS

This invention was made in part with government support under ContractNo. F29601-00-C-0158 between the U.S. Missile Defense Agency andGratings Incorporated, a New Mexico corporation. The government hascertain rights in the invention.

FIELD OF THE INVENTION

The present invention relates generally to solar cells andphotodetectors and, more particularly, to enhancement of absorption andtolerance to ionizing radiation, resulting from surface random andperiodic microstructures formed from the material of the solar cell orphotodetector for thin film (<50 μm) solar cells and photodetectors.

BACKGROUND OF THE INVENTION

Since its inception more than fifty years ago, silicon (Si) photovoltaic(PV) technology has been a reliable source of power for military andcommercial satellites in space (See, e.g., P. Iles in Progress inPhotovoltaics: Research and Applications, Vol. 2, 95 (1994)). However,more recently, the III-V compound semiconductor technology has developedwith the availability of high-throughput thin film deposition systems ongermanium substrates and subsequent fabrication of high- efficiency(˜25%), multi-junction solar cells (See, e.g., P. R. Sharps, et al.,IEEE PVSC 23, 650 (1993)).

Silicon (Si) solar cells for use in space environments have notexperienced comparable improvements and, as a result, have lost asignificant market share to the compound semiconductor multi-junctionsolar cell technology. However, radiation-tolerant Si solar cells withefficiencies (˜20-25%) remain a viable option for several spaceapplications including nanosatellites, unmanned space vehicles, andcommercial satellites not requiring high efficiencies (See, e.g., P.Iles in Progress in Photovoltaics: Research and Applications, Vol. 8,2864 (2000)). Additionally, thin-film Si solar cells also offersignificant cost savings in manufacturing and launch expenses (See,e.g., J. Tringe et al., IEEE PVSC 28, 1242 (2000)). The performance ofSi solar cells in space environments is severely degraded due toradiation of high-energy particles and electromagnetic radiation (See,e.g., M. Y. Yamaguchi, et al., Appl. Phys. Lett. 68, 3141 (1996)). Theradiation-induced surface and volume damage creates volume recombinationcenters and reduces minority carrier diffusion lengths, resulting in asignificant reduction of the cell performance in the near infrared (IR)region (See, e.g., L. Prat et al., Solar Cells 31, 47 (1991)).Improvements in Si space solar cells have been achieved by incorporationof back surface fields, surface texturing, fine grid spacing, andthinner substrates (See e.g., A. Suzuki et al., IEEE Trans. Elect. Dev.46, 2126 (1999)). It has been well established that tolerance toionizing radiation-induced recombination losses of Si solar cells issignificantly improved by reducing cell thickness (See, e.g., S.Matsuda, et al., ESA, SP 320, 609 (1991)). Decreasing Si thickness alsolowers weight.

Ideally, the cell optimum thickness is a fraction of the minoritycarrier diffusion length (See, e.g., H. J. Hovel, Solar Cells,Semiconductors and Semimetals, Vol. II. Academic press (1975)). However,in the near IR (˜0.9-1.11-μm) wavelength range, optical absorption in Siis weak (See, e.g., M. A. Green and M. J. Keevers, Progress inPhotovoltaics: Research and Applications, Vol. 3, 189 (1995)). Random,wet-chemical texturing techniques have been used to form pyramids in the(100) Si crystal orientation for reducing reflection and enhancingoptical absorption by increased oblique coupling into the solar cells(See, e.g., P. Campbell and M. A. Green, Appl. Phys. Lett. 62, 243(1987)). Applicability of these texturing schemes to thin wafer andfilms (˜20-50 μm) is limited due to their large dimensions andpreferential (100) crystal etching mechanisms.

Alternate approaches based on subwavelength random, or periodicmicroscopic structures aimed at reflection reduction and enhancednear-IR absorption have been extensively investigated. Randomly texturedsubwavelength surfaces reduce broadband reflection to <5% and enhancenear-IR absorption through increased oblique coupling of light into thesemiconductor (See, e.g., Saleem H. Zaidi et al., IEEE Trans. Elect.Dev. 48, 1200 (2001)). Random subwavelength surfaces represent a Fouriersummation of a wide range of periodic microscopic structures, theenhanced near-IR absorption from such surfaces results from diffractivecoupling of light as opposed to refractive oblique coupling ingeometrically textured surfaces.

In contrast with random subwavelength microscopic structures, periodicsubwavelength microscopic structures offer highly controllablemechanisms aimed at Si reflection and absorption response over a widespectral range. T. K. Gaylord et al. in Appl. Opt. 25, 4562 (1986) havedescribed rigorous models of rectangular profiled grating microscopicstructures exhibiting zero reflection for a suitable choice of gratingparameters. D. H. Raguin and G. M. Morris in Appl. Opt. 32, 1154 (1993)have determined broadband anti-reflection properties of 1D triangularand 2D pyramidal surfaces. Ping Shen et al. in Appl. Phys. Lett. 43, 579(1983) have reported wavelength-selective absorption enhancement ofthin-film (˜2 μm) amorphous Si solar cells by grating coupling intowaveguide modes. C. Heine and R. H. Morf in Appl. Opt. 34, 2478 (1983)have demonstrated enhanced near IR absorption in ˜20-μm thick Si filmsby diffractive coupling. Broadband and narrowband spectral reflectionresponse of subwavelength Si grating microscopic structures has beenreported by Saleem H. Zaidi et al. in J. Appl. Phys. 80. 6997 (1996).Enhanced near IR response of subwavelength grating solar cells has alsorecently been demonstrated by Saleem H. Zaidi et al., in IEEE PVSC 28,395 (2000).

Gaylord et al., supra, describes the anti-reflection properties of 1Drectangular grating microscopic structures; however, the need to createabsorption close to the solar cell junction particularly in near IRspectral range is not discussed. Heine and Morf, supra, describe adiffractive approach directed at improving solar cell response at λ˜1.0μm. For thin-film solar cells, near IR absorption is weak due to theindirect bandgap of Si. By fabricating a grating structure at the backsurface of the cell, enhanced absorption can be achieved by efficientcoupling of the incident beam into two diffraction orders for asymmetric profile, or a single diffraction order for a blazed profile.Heine and Morf teach away from the use of a front surface gratingbecause of surface passivation issues. By proper design of gratingparameters, Heine and Morf have chosen the direction of propagation ofdiffraction orders such that at angles larger than the critical angle,these orders are trapped as a result of total internal reflection.

The concept of improving electron-hole pair (EHP) collection in thevolume of a solar cell using deeply etched trenches was investigated in(110) Si solar cells for the purpose of improving radiation tolerance(See, e.g., John Wohlgemuth and A. Scheinine, IEEE PhotovoltaicSpecialists Conference, page 151 (1980)). Because of the preferentialetch differential between <111> and <110> planes, simple wet-chemicaletching chemistry can be employed to form one-dimensional trenches in(110) Si (See, e.g., Saleem H. Zaidi et al., J. Appl. Phys. 80, 6997(1996). In IEEE PVSC 28, 1293 (2000) trenches formed in (100) Si usingdeep reactive ion etching techniques were investigated by H. Presting etal. The structures employed were macroscopic (>> optical wavelengths)and the observed improvements were marginal, presumably, the result of alack of enhanced near-IR absorption. In both (110) Si vertical grooves,and (100) Si deep random ion etching (DRIE) trenches, a significantfraction of the EHPs generated in the volume of the cell is lost torecombination due to the inability of the material to absorb near IRradiation near the junction areas.

Accordingly, it is an object of the present invention to improve lightabsorption in thin films (<50 μm) used as solar cells and photodetectorsin the near-IR spectral range.

Another object of the present invention is to enhance volume collectionof electron/hole pairs in solar cells and photodetectors used in thepresence of ionizing radiation.

Additional objects, advantages and novel features of the invention willbe set forth, in part, in the description that follows, and, in part,will become apparent to those skilled in the art upon examination of thefollowing or may be learned by practice of the invention. The objectsand advantages of the invention may be realized and attained by means ofthe instrumentalities and combinations particularly pointed out in theappended claims.

SUMMARY OF THE INVENTION

To achieve the foregoing and other objects of the present invention, andin accordance with its purposes, as embodied and broadly describedherein, the method for forming thin film solar cells and photodetectorshaving increased light absorption and radiation tolerance hereofincludes: forming a plurality of macroscopic features having a chosenperiodic spacing, width and depth on a first surface of a doped filmsuitable for solar cell or photodetector applications and formedtherefrom, each feature having at least one surface perpendicular to thefirst surface of the film and one surface parallel thereto, there alsobeing formed surfaces between each of the plurality of macroscopicfeatures; attaching an electrical contact to at least a portion of asecond surface of the film, the second surface being generally parallelto and spaced apart a chosen thickness from the first surface; dopingthe region of the surfaces of the plurality of macroscopic features andthe region of the surfaces between each of the plurality of macroscopicfeatures, forming thereby a p-n junction with the doped film; attachingan electrical contact to at least a portion of the junction, whereby thefilm is adapted to produce a photovoltaic response to light having achosen wavelength or wavelengths incident thereon, the period of themacroscopic features, the width and the depth thereof and the thicknessbetween the first and second surfaces of the film being chosen such thatminority carrier diffusion length for carriers produced by thephotovoltaic response of the film is larger than the largest distancebetween a location interior to the film and the junction; and randomlyetching 3-dimensional microscopic structures having dimensions less thanthe wavelength or wavelengths of light onto the surfaces of themacroscopic features which are parallel to the surface of the film, ontothe surfaces between each of the plurality of macroscopic features andonto the surfaces of each macroscopic feature perpendicular to the firstsurface of the film, such that light incident thereon is scattered intoa multiplicity of high diffraction orders which propagate obliquely tothe direction of incidence of the light, thereby trapping the incidentlight by total internal reflection and increasing light absorption bythe film.

In another aspect of the present invention, in accordance with itsobjects and purposes, the method for forming solar cells andphotodetectors having increased light absorption and radiation tolerancehereof includes: forming a plurality of macroscopic features having achosen periodic spacing, a chosen width and a chosen depth on a firstsurface of a doped film suitable for solar cell and photodetectorapplications and formed therefrom, each feature having at least onesurface perpendicular to the first surface of the film and one surfaceparallel thereto, there also being formed surfaces between each of theplurality of macroscopic features; attaching an electrical contact to atleast a portion of a second surface of the film, the second surfacebeing generally parallel to and spaced apart a chosen thickness from thefirst surface; doping the region of the surfaces of the plurality ofmacroscopic features and the region of the surfaces between each of theplurality of macroscopic features, thereby forming a p-n junction withthe doped film; attaching an electrical contact to at least a portion ofthe doped surfaces, whereby the film is adapted to produce aphotovoltaic response to light having a chosen wavelength or wavelengthsincident thereon, the period of the macroscopic features, the width andthe depth thereof, and the thickness between the first and secondsurfaces of the wafer being chosen such that minority carrier diffusionlength for carriers produced by the photovoltaic response of the film islarger than the largest distance between a location interior to the filmand the junction; and generating a microscopic grating structure havinga second chosen period on the surface of each macroscopic featureparallel to the first surface of the film and on the surfaces of eachmacroscopic feature perpendicular to the first surface of the film,wherein the second chosen period is smaller than the chosen period ofthe macroscopic features, whereby incident light thereon is distributedinto higher diffraction orders which are trapped within the macroscopicfeatures.

In yet another aspect of the invention, in accordance with its objectsand purposes, the method for forming solar cells and photodetectorshaving increased light absorption and radiation tolerance hereofincludes: forming a microscopic grating structure having a chosen periodand chosen depth on a first surface of a doped film suitable for solarcell and photodetector applications; attaching an electrical contact onat least a portion of a second surface of the film, the second surfacebeing generally parallel to and spaced apart a chosen thickness from thefirst surface, wherein the chosen depth of the grating structure iscomparable to the chosen thickness of the film; doping the surfaces ofthe generated microscopic grating structure, forming thereby a p-njunction with the film; and attaching an electrical contact to at leasta portion of the doped surfaces of the generated microscopic gratingstructure, whereby the film is adapted to produce a photovoltaicresponse to light having a chosen wavelength or wavelengths incidentthereon, the chosen period of the microscopic grating structure and thethickness between the first and second surfaces of the film being chosensuch that minority carrier diffusion length for carriers produced by thephotovoltaic response of the film is larger than the largest distancebetween a location interior to the film and the junction.

In still another aspect of the present invention in accordance with itsobjects and purposes, the photovoltaic device having increased lightabsorption and radiation tolerance hereof includes, which comprises incombination: a doped film suitable for photovoltaic applications; aplurality of macroscopic features having a chosen periodic spacing, achosen width and a chosen depth formed on a first surface of the filmfrom the film, each feature having at least one surface perpendicular tothe first surface of the film and one surface parallel thereto, therealso being formed surfaces between each of the plurality of macroscopicfeatures, and the region of the surfaces of the plurality of macroscopicfeatures and the region of the surfaces between each of the plurality ofmacroscopic features being doped, forming thereby a p-n junction withthe film; an electrical contact attached to at least a portion of asecond surface of the film, the second surface being generally parallelto and spaced apart a chosen thickness from the first surface thereof;an electrical contact attached to at least a portion of the junction,whereby the film is adapted to produce a photovoltaic response to lighthaving a chosen wavelength or wavelengths incident thereon, the periodof the macroscopic features, the width and the depth thereof, and thethickness between the first and second surfaces of the film being chosensuch that minority carrier diffusion length for carriers produced by thephotovoltaic response of the film is larger than the largest distancebetween the junction and a location within the film; and a randomlyetched 3-dimensional microscopic structure having dimensions less thanthe wavelength or wavelengths of light disposed on the surfaces of themacroscopic features which are parallel and perpendicular to the surfaceof the film and on the surfaces between each of the plurality ofmacroscopic features such that light incident thereon is scattered intoa multiplicity of high diffraction orders which propagate obliquely tothe direction of incidence of the light, thereby trapping the incidentlight by total internal reflection and increasing light absorption bythe film.

In a further aspect of the invention, in accordance with its objects andpurposes, the photovoltaic device having increased light absorption andradiation tolerance hereof, includes: a doped film suitable forphotovoltaic applications; a plurality of silicon macroscopic featureshaving a chosen periodic spacing, a chosen width and a chosen depthformed on a first surface of the film, each feature having at least onesurface perpendicular to the first surface of the film and one surfaceparallel thereto, there also being formed surfaces between each of theplurality of macroscopic features; an electrical contact attached to atleast a portion of a second surface of film, the second surface beinggenerally parallel to and spaced apart a chosen thickness from the firstsurface, and the region of the surfaces of the plurality of macroscopicfeatures and the region of the surfaces between each of the plurality ofmacroscopic features being doped, forming thereby a p-n junction withthe film; an electrical contact attached to at least a portion of thejunction, whereby the film is adapted to produce a photovoltaic responseto light having a chosen wavelength or wavelengths incident thereon, theperiod of the macroscopic features, the width and the depth thereof andthe thickness between the first and second surfaces of the film beingchosen such that minority carrier diffusion length for carriers producedby the photovoltaic response of the film is larger than the largestdistance between a location interior to the film and the junction; and amicroscopic grating structure having a second chosen period formed onthe surfaces of each of the macroscopic features parallel andperpendicular to the first surface of the film wherein the second chosenperiod is smaller than the chosen period of the macroscopic features,whereby incident light thereon is distributed into higher diffractionorders which are trapped within the macroscopic features.

In another aspect of the invention, in accordance with its objects andpurposes, the photovoltaic device having increased light absorption andradiation tolerance hereof, includes: a doped film suitable forphotovoltaic applications; a microscopic grating structure having achosen period, a chosen width and chosen depth formed on a first surfacethe film, the surfaces of the grating structure being doped, formingthereby a p-n junction with the film; an electrical contact attached toat least a portion of a second surface of the film, the second surfacebeing generally parallel to and spaced apart a chosen thickness from thefirst surface, wherein the chosen depth of the microscopic gratingstructure is approximately equal to the chosen thickness of the film;and an electrical contact attached to at least a portion of the dopedsurfaces of the grating structure, whereby the film is adapted toproduce a photovoltaic response to light having a chosen wavelength orwavelengths incident thereon, the chosen period of the grating structureand the thickness between the first and second surfaces of the filmbeing chosen such that minority carrier diffusion length for carriersproduced by the photovoltaic response of the film is larger than thelargest distance between a location interior to the film and thejunction.

Benefits and advantages of the present method include photovoltaicdevices having enhanced optical absorption and enhanced tolerance toionizing radiation for solar cell, space solar cell, andwavelength-selective photodetector applications, where enhanced IRresponse is required as a result of either insufficient film thicknessfor absorption or radiation-induced volume damage leading tolow-lifetime material.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated in and form a part ofthe specification, illustrate the embodiments of the present inventionand, together with the description, serve to explain the principles ofthe invention. In the drawings:

FIG. 1 is a schematic representation of one embodiment of theradiation-tolerant, thin-film silicon photovoltaic device of the presentinvention, showing subwavelength random microscopic structures etchedonto the active light absorbing regions of the front and back surfacesof the thin film.

FIG. 2 is a schematic representation of a second embodiment of theradiation-tolerant, thin-film silicon photovoltaic device of the presentinvention showing subwavelength random microscopic structures etchedonto the front, sidewall and back surfaces of the thin film.

FIG. 3 is a schematic representation of a third embodiment of theradiation-tolerant, thin-film silicon photovoltaic device of the presentinvention showing subwavelength periodic microscopic structures etchedonto the active light absorbing regions of the front and back surfacesof the thin film.

FIG. 4 is a schematic representation of a fourth embodiment of theradiation-tolerant, thin-film silicon photovoltaic device of the presentinvention showing subwavelength periodic microscopic structures etchedon the front, vertical sidewalls, and back surfaces of the thin film.

FIG. 5 is a schematic representation of a fifth embodiment of theradiation-tolerant, thin-film silicon photovoltaic device of the presentinvention showing inverted pyramids formed in the deep-etched portionsof the film surface and front and back surfaces either beingperiodically or randomly textured.

FIGS. 6 a-6 c illustrate three optical configurations for whichabsorption calculations have been performed for silicon thin-films;where FIG. 6 a is planar reference film, FIG. 6 b is a grating structureetched the majority of the way through the thin film, and FIG. 6 c is agrating structure partially etched through the thin film.

FIGS. 7 a and 7 b are graphs of calculated optical absorption as afunction of wavelength for silicon on an aluminum substrate, FIG. 7 ashowing planar films having several thicknesses and FIG. 7 b showinggrating microscopic structures having several depths etched the majorityof the way through to the aluminum substrate.

FIG. 8 a is a graph of optical absorption as a function of wavelengthfor several thicknesses and depths of a one-dimensional (1D) silicongrating with an underlying silicon thin film on an aluminum substrate,while FIG. 8 b is a graph of the averaged optical absorption as afunction of film thickness for the 3, thin-film configurations shown inFIGS. 6 a-6 c hereof.

FIG. 9 a is a graph of the optical absorption as a function ofwavelength for two-dimensional (2D) silicon gratings having severalthicknesses on an underlying silicon film on an aluminum substrate,while FIG. 9 b is a graph of the averaged optical absorption for thethree, 2D thin-film grating thickness/thin film thickness combinations.

FIG. 10 is a graph of the optical absorption of 1D and 2D silicongrating microscopic structures having underlying films as a function ofwavelength compared with the optical absorption of the underlyingsilicon film, the optical absorption in the 15-μm thickness with a 2Dgrating structure being higher than that for the 50-μm thick 1D gratingstructure.

FIG. 11 is the output of a scanning electron microscope (SEM) forrandomly textured, subwavelength 2D microscopic structures etched insilicon.

FIGS. 12 a-12 d are SEM outputs for different profiles etched in (100)silicon: (a) ˜0.3-μm period triangular profile; (b) 1.0-μm periodrectangular profile, (c) 2D post pattern having an 0.8-μm period; and(d) 2D hole pattern having an 0.8-μm period.

FIGS. 13 a-13 f are SEM outputs for deeply etched 1D and 2D gratingstructures silicon, where the structure shown in FIG. 13 a is 20-μm deepwith a 10-μm period; the structure shown in FIG. 10 b is 10-μm deep witha 1.6-μm period; the structure shown in FIG. 10 c is 7-μm deep with a0.8-μm period; the structure shown in FIG. 10 d is a 10-μm deep holepattern having a 10-μm period; the structure shown in FIG. 10 e is an8-μm deep hole pattern having a 1.6-μm period; and the structure shownin FIG. 10 f is a 3.5-μm deep hole pattern having a 0.8-μm period.

FIGS. 14 a and 14 b are SEM outputs for etch and deposition cycles,where the structure shown in FIG. 14 a is formed by two etch and onedeposition cycles, and the structure shown in FIG. 10 b is formed byfour etch and three deposition cycles.

FIGS. 15 a-15 c are SEM outputs for several periodic subwavelengthmicroscopic structures on the sidewalls of a 1D grating.

FIGS. 16 a and 16 b are SEM outputs for randomly textured subwavelengthmicroscopic structures on the sidewalls of a 1D grating structure.

FIGS. 17 a and 17 b are SEM outputs for anodically etched surfaces: FIG.17 a having features with ˜0.05 μm width, ˜0.1 μm spacing, and ˜8 μmdepth; and FIG. 17 b having features with ˜0.35-μm diameter and a depthof ˜13 μm.

FIG. 18 is a graph of hemispherical spectral reflectance from randomlydistributed subwavelength silicon surfaces as a function of wavelength.

FIG. 19 is a graph of hemispherical spectral reflectance from 1D, 0.5 μmperiod subwavelength silicon grating surfaces as a function ofwavelength.

FIG. 20 is a graph of one sun LIV measurements under AM0 conditions from˜1 μm deep, 1D grating solar cells FIG. 21 is a graph of one sun LIVmeasurements under AM0 conditions from ˜10 μm deep, 2D grating solarcells.

FIG. 22 is a graph of one sun LIV measurements under AM0 conditions from˜10-μm deep 1D grating solar cells.

FIGS. 23 a and 23 b are graphs of spectral response from 1D (FIG. 23 a)and 2D (FIG. 23 b) grating solar cell structures formed using deepreactive ion etching to an approximately 10-μm depth, as a function ofwavelength.

FIG. 24 is a graph of internal quantum efficiency from randomlydistributed, subwavelength-structured solar cells formed usinggas-source diffusion; planar surface response is shown for comparison.

FIG. 25 is a graph of internal quantum efficiency from randomlydistributed, subwavelength-structured solar cells formed usingion-implanted diffusion as a function of wavelength; planar surfaceresponse is shown for comparison.

FIG. 26 a is a schematic representation of a thin-film silicon solarcell having periodic and/or random subwavelength microscopic structureson the front, sidewalls, and back surface with the active area havingbeen reduced, and FIG. 26 b is an SEM output for KOH-thinning of asilicon wafer from approximately 500-μm thickness to about 300-μm.

DETAILED DESCRIPTION

Briefly, the present invention includes the use of subwavelength randomand periodic microscopic structures for enhancing light absorption andimmunity to ionizing radiation damage of thin-film solar cells andphotodetectors, hereinafter being referred to as photovoltaic devices.Front surface random and periodic microscopic structures can beclassified either as diffractive or waveguide elements. Diffractivefront surface microscopic structures scatter light into obliquepropagating higher diffraction orders that are effectively trappedwithin periodic surface features etched through the majority of the thinfilm. The microscopic periodic surface features further enhanceabsorption by acting as light waveguides perpendicular to the solar cellsurface. Typically, the photovoltaic devices of the present inventionhave dimensions as follows: thin film thickness is between 15 μm and 50μm, and the plurality of surface features each have a chosen widthbetween 1 μm and 50 μm, a depth of between 10 μm and 30 μm, and aspacing of between 0.5 μm and 5 μm.

The enhanced radiation tolerance of these structures is due to closelyspaced, vertical sidewall p-n or n-p junctions that capture a majorityof deeply generated electron-hole pairs before they are lost torecombination. The separation of these vertical sidewall junctions issmaller than the minority carrier diffusion lengths even afterradiation-induced degradation. The various optical structures andconfigurations described here can be easily fabricated by employingwell-known laser-interferometric lithography, anodic etching, reactiveion etching, and PECVD oxide deposition techniques. Surface damageduring reactive ion etching (RIE) processes can be eliminated by furtherselective etching employing dry- or wet-chemical etching processes.RIE-induced surface damage can also be eliminated by use ofion-implanted junctions. Plasma immersion doping techniques can be usedto from junctions on deeply etched sidewalls, as can gas source, orsolid source diffusions after RIE-damage removal treatments. Thethin-film space solar cells of the present invention are expected tooffer superior resistance to radiation and have significantly reducedweight due to removal of a majority of the photovoltaic material byetching.

Thus, in accordance with the teachings of the present invention, arandom, and/or periodic subwavelength structure is etched through asignificant fraction of the active region of a thin-film photovoltaicmaterial such that light entering the volume of the material ispredominantly absorbed within these deeply etched structures. Acompromise is made between choosing a film thickness sufficiently narrowthat ionizing radiation damage is minimized, while retaining sufficientlight absorption by the remaining photovoltaic materials. This latterpurpose is served by use of subwavelength (distances smaller than thewavelength of the incident light) non-periodic and periodic macroscopicsurface structures to increase optical pathlengths, and microscopicstructures to increase light absorption by waveguide-coupling.

Reference will now be made in detail to the present preferredembodiments of the invention examples of which are illustrated in theaccompanying drawings. In what follows, identical callouts will be usedfor similar or identical structure.

Turning now to FIG. 1 hereof, a typical photovoltaic device, 10,designed in accordance with the teachings of the present invention isschematically illustrated. Three-dimensional periodic macroscopicfeatures, 12 a and 12 b, are etched deeply into a thin film ofphotovoltaic material, 14, using procedures set forth hereinbelow toreceive incident light. Typically, the thin film 14 comprises n- orp-doped silicon or gallium arsenide, shown in FIG. 1 between 15 μm and50 μm thickness, 16, and surface features 12 a and 12 b each have achosen width, 18, between 1 μm and 50 μm, a depth, 20, between 10 μm and30 μm, and a spacing, 22, of between 0.5 μm and 5 μm. The surfaces, 24,receiving the incident light are n-doped (p-doped, if the film isn-doped silicon), 26. To enhance scattering into the photovoltaicmaterial, and to reduce reflection, the surfaces receiving light, 24,and rear surface, 28, are randomly textured, 30 a and 30 b, and 32,respectively. The dimensions of the 3D volume periodic structure on thefront surface of the solar cell are selected such that electron-holepairs generated internal to the photovoltaic material, 34 , by theincident light are collected by the vertical sidewall junctions, 36 aand 36 b, prior to recombination due to any radiation-induced volumedamage in the material. Front-surface electrical contact, 38, andrear-surface electrical contact, 40, permit voltages to be measured andcurrents withdrawn from the photovoltaic material in accordance withstandard measurement procedures.

FIG. 2 shows random texturing, 42, having been added to the sidewalls ofmacroscopic features 12 a and 12 b, and to the front surface, 44, offilm 14.

FIG. 3 shows another embodiment of the invention where similarobjectives are achieved by replacing front and rear surface randomtexturing with suitably designed subwavelength grating microscopicstructures, 46 a and 46 b, for diffracting the incident light intohigher order modes which propagate in directions away from the normal tothe surface of incidence, thereby improving absorption thereof.

The embodiment shown in FIG. 4 includes grating microscopic structures,48 a and 48 b, along the vertical sidewalls of macroscopic features 12 aand 12 b, respectively, and to the front surface, 50, of thin film 14.

FIG. 5 shows another embodiment for enhancing light trapping and carriercollection by forming several pyramids, 52 a and 52 b along thesidewalls of the feature structure, 12 a and 12 b, respectively.

In the photovoltaic device embodiments shown in FIGS. 1-5, hereof, lighttrapping is based on considerations of diffractive optics. Random, orperiodic subwavelength microscopic structures scatter incident lightinto obliquely propagating diffraction orders that enhance absorptiondue to confinement by total internal reflection. The 3D macroscopicfeatures 12 a and 12 b, formed for carrier collection, have smallerdimensions than minority carrier diffusion lengths.

For periodic microscopic structures smaller, or comparable in size tooptical wavelengths, enhanced light absorption is achieved by waveguidemechanisms. For these microscopic structures, grating linewidths are≦1.0 μm, and absorption is primarily within the individual gratinglines. Because the electron-hole pairs are generated within ≦1-μm fromthe junctions, these cells are expected to be supremelyradiation-tolerant provided high-quality shallow (<0.1-μm) junctions canbe formed.

FIG. 6 shows two thin-film optical configurations for solar cells withsubwavelength periodic grating microscopic structures, a planar filmstructure is shown for reference. FIGS. 6 a-6 c illustrate three opticalconfigurations for which absorption calculations have been performed forsilicon thin-films. FIG. 6 a is planar reference film, FIG. 6 b shows agrating structure etched the majority of the way through the thin film,while FIG. 6 c shows a grating structure partially etched through thethin film.

1. Radiation-Tolerant Thin-Film Solar Cell Configurations

a. Optical Confinement Using Diffractive Optics:

In order to enhance radiation tolerance of silicon solar cells in space,two technical issues have to be addressed:

(i) design of optical structures aimed for achieving complete lightabsorption in thin (≦50 μm) film structures, particularly in the near-IR(λ˜0.9-1.1 μm) spectral region; and

(ii) generation of three-dimensional (3D) emitter formations forcollection of photo-generated electron-hole pairs in the surface andvolume regions prior to recombination.

Enhanced near-IR absorption can potentially be achieved by completerandomization of the transmitted light inside a weakly absorptivemedium. Yablonovitch has shown absorption enhancement in a weaklyabsorptive medium by as as 4n² over a planar sheet, where n is therefractive index (See e.g., E. Yablonovitch, J. O. S. A. 72, 899(1982)). Diffractive scattering of light by subwavelength microscopicstructures helps realize this statistical limit (See e.g., H. W. Deckmanet al., Appl. Phys. Lett. 42, 968 (1983)). Since a subwavelength randomstructure is a superposition of several grating periods having a widerange of profiles and depths, light incident on such a surface isdiffractively coupled into many obliquely propagating beams leading toincreased optical path lengths and absorption probabilities.

Enhanced EHP collection can be achieved by forming p-n junctions in thevolume of the thin-film device regions to reduce the distancephoto-generated carriers travel prior to collection at the junction. Forexample using low-cost optical lithography, anodic etching, and reactiveion etching techniques, p-n junction grid can be spaced to ˜5-μm gridspacing, and etched through the entire thickness of the film

FIG. 1 illustrates a typical top and bottom-contact thin-film solarcell. The front and back surface contacts are formed using appropriatemetal stacks (see e.g., A. H. Fahrenbruch and R. H. Bube in Fundamentalsof Solar Cells, Academic Press (1983)). Subwavelength random texture onfront and back surfaces is combined with a macroscopic periodic gridaimed at collection of photo-generated electron-hole pairs. A junctionis formed on the front surface following subwavelength random texturing,the doping type is opposite to the film doping. For instance, if thewafer is p-type, the junction will be n-type and vice versa. FIG. 2describes another thin-film top and bottom-contact solar cell. Incomparison with the cell structure described in FIG. 1, thesubwavelength randomly textured microscopic structures are also extendedto the sidewalls. This configuration will enhance light trapping due todiffractive scattering between top and bottom planes (z-axis), and in-plane scattering; that is, enhanced scattering in xy-plane.

FIG. 3 describes a thin-film cell configuration in which randomsubwavelength microscopic structures at the top and bottom surfaces arereplaced by periodic microscopic structures. The thin-film solar cellstructure in FIG. 4 is similar to that in FIG. 3 except for theextension of periodic microscopic structures to sidewalls. Periodicmicroscopic structures can be beneficially used for enhanced near IRlight absorption (See e.g., Saleem H. Zaidi, J. M. Gee, and D. S. Rubyin IEEE PVSC-28, 395 (2000)).

FIG. 5 shows a novel optical confinement scheme in which invertedpyramids are formed along the volume of the thin-film structure. Most ofthe transmitted light within such surfaces is optically confined due tototal internal reflection.

b. Optical Confinement using Waveguide and Physical Optics:

For subwavelength periodic silicon microscopic structures etched througha thin film, enhanced light absorption resulting from waveguide andphysical optics mechanisms can also be achieved. Light absorption insuch microscopic structures was investigated using the commerciallyavailable grating modeling software GSOLVER™. FIG. 6 shows the threethin-film configurations: (a) planar; (b) grating only; and (c)composite grating and thin film structure, employed for absorptioncalculations. The back surface aluminum reflector serves both as thereflector and the back surface contact.

Optical absorption as a function of wavelength for various filmthicknesses and grating depths is shown in FIG. 7. Absorptioncalculations are for 1D grating microscopic structures (FIG. 7 b), witha 50% duty cycle, 0.8-μm period, and un-polarized, normally incidentlight. FIG. 7 shows that absorption increases as a function of filmthickness, and reaches saturation for planar film thickness in˜100-200-μm range. For a 1D grating structure, absorption saturates atdepths of ˜50 μm. FIG. 8 a is a graph of optical absorption as afunction of wavelength for the composite grating structure. In thiscase, absorption saturates for grating depths in ˜25-45-μm range. FIG. 8b plots averaged optical absorption as a function of thickness for thethree configurations shown in FIG. 6. To be noticed is that the highestabsorption is achieved for the composite grating and thin filmconfiguration (FIG. 6 c).

Since the sunlight is randomly polarized, it is important to evaluatetwo-dimensional grating microscopic structures, so that polarizationeffects are minimized. FIG. 9 a is a graph of optical absorption for 2D,0.8-μm period grating microscopic structures. To be noticed is that asthe grating depth increases, the increase in absorption is more rapidthan for the 1D grating case. FIG. 9 b is a graph of the opticalabsorption for the composite case. Here the variation of absorption withgrating depth is not as great. Comparison of absorption in 1D and 2Dmicroscopic structures reveals that significantly higher absorption isachieved for the 2D patterns. FIG. 10 is a graph of absorption as afunction of wavelength for planar, 1D, and 2D grating microscopicstructures. It may be observed that the planar film has lowestabsorption, and that a 2D pattern can achieve greater absorption whencompared with 1D structure at ⅓ of the 1D composite film and gratingthickness.

2. Fabrication of Subwavelength Microscopic Structures in Silicon

Random and periodic subwavelength microscopic structures can beconveniently formed using reactive ion etching and lithographytechniques. Random reactive ion texturing techniques aimed at reducingsilicon reflection and enhancing near-IR absorption have beenextensively investigated for terrestrial solar cell applications (See,e.g., Saleem H. Zaidi, et al., IEEE Trans. Elect. Dev. 48, 1200 (2001)).FIG. 11 hereof shows a scanning electron microscope (SEM) output of arandomly textured silicon surface generated using reactive ion etchingin an SF₆/O₂ plasma. Typical process parameters were: SF₆=14 sccm; O₂=16sccm; pressure=170 mTorr; and Power=300 W. These types of microscopicstructures are easily fabricated on the front and back surfaces ofsilicon solar cells as is described in FIGS. 3 and 4 hereof.

Subwavelength periodic grating microscopic structures can be mostconveniently fabricated using laser interference techniques. A. Malag inOpt. Commun. 32, 54 (1980), and Saleem H. Zaidi and S. R. J. Brueck, inAppl. Opt. 27 (1988) describe typical fabrication techniques for simpleone and two-dimensional microscopic structures. Interference between twocoherent laser beams produces a simple periodic pattern at d=λ/2 sin θ,where λ is the exposure wavelength, and 2θ is the angle between the twointersecting laser beams. For λ=0.355 μm, θ=60°, periods down to ˜0.2 μmcan easily be fabricated. Typically, grating microscopic structures arefirst formed in photoresist followed by pattern transfer to siliconusing an appropriate combination of wet and dry etching techniques.Silicon reactive ion etching (RIE) techniques have been very wellcharacterized, see, for example, P. M. Kopalidis and J. Jorne in J.Electrochem. Soc., Vol. 139 (1992) on Si etching in SF₆/O₂ plasmas.Wet-chemical etching of Si is also very well understood; see, forexample K. E. Bean in IEEE Trans. Elect. Dev., ED 25, 1185 (1978).

FIG. 12 shows SEM outputs for typical 1D and 2D grating microscopicstructures. One-dimensional, triangular and rectangular profiles areshown in FIGS. 12 a and 12 b, respectively, and were formed by KOH andSF₆/O₂ reactive ion etching, respectively. For wet-chemical etching, a40% KOH solution was used at room temperature. For reactive ion etchingthese gratings, the room temperature etching parameters were as follows:SF₆=14 sccm; O₂=12 sccm; pressure=50 mTorr; RF Power=50 Watt. The etchmasks used were SiO₂ and Cr (˜30 nm thick) respectively. Two-dimensionalpost and hole patterns formed using the same reactive ion etchingparameters are shown in FIGS. 12 c and 12 d, respectively.

a. Deep Reactive Ion Etched Subwavelength Microscopic Structures:

Enhanced near-IR optical absorption and increased radiation tolerance isachieved by closely spaced, deeply (˜10-50 μm) etched structures. Recentadvancements in reactive ion technology make it possible to form suchstructures. FIG. 13 shows some examples of these deep reactive ionetched (DRIE) structures. FIG. 13 a shows a 10-μm period, 1D patternetched to a depth of ˜20 μm, FIG. 13 b shows a 1.6-μm period 1D gratingetched to a depth of ˜10 μm, FIG. 13 c shows a 0.8-μm period 1D gratingetched to depth of ˜7 μm, FIG. 13 d shows a 10-μm period, 2D holepattern etched to a depth of 10 μm, FIG. 13 e shows a 1.6-μm period, 2Dhole pattern etched to depth of ˜8 μm, and finally FIG. 13 f shows a0.8-μm period 2D hole pattern etched to depth of 3.5 μm. Thesestructures demonstrate the feasibility of device concepts outlined inFIGS. 1-6.

Techniques to form deeply etched grating microscopic structures based onlow-cost, multiple etch and deposition cycles have been developed. FIG.14 shows two examples of these etch and deposit reactive ion etchingcycles. FIG. 14 a shows grating structure formed using two reactive ionetchings and one plasma enhanced chemical vapor deposition (PECVD) oxideprocess; a reactive ion etching (RIE) step is followed by PECVD oxidedeposition, followed by a second reactive ion etch step. The PECVD oxidedeposition parameters used were: pressure=5400 mTorr; SiH₄=400 sccm;N₂O=450 sccm; He=450 sccm; and RF power=30 Watt. The oxide film on thesidewalls is required to prevent lateral etching, and helps achievealmost vertical sidewalls. FIG. 14 b shows grating profiles formedfollowing four RIE and three PECVD deposition steps. These resultsdemonstrate that the device microscopic structures proposed in FIGS. 1-6can be fabricated by a suitable combination of RIE and PECVD oxidedeposition steps.

The RIE and deposition processing sequences outlined in FIG. 14 alsoallow periodic sidewall microscopic structures having desiredperiodicity and profiles to be generated. FIG. 15 shows examples ofvertical grooved sidewall microscopic structures formed by a combinationof reactive ion etching, PECVD deposition and KOH etching. To beobserved is that only two KOH cycles were employed in FIGS. 15 a and 15b, and one in FIG. 15 c. By repeating these etch and deposition cycles,periodic gratings can be etched all the way through a thin filmstructure. FIG. 16 shows formation of random subwavelength microscopicstructures on the vertical sidewalls similar to the front surfacemicroscopic structures shown in FIG. 11.

b. Anodic Etching Techniques for Subwavelength Microscopic Structures:

The electrochemical etching of Si in HF solutions is a well-known methodfor porous Si formation (See, e.g., D. R. Turner, J. Electrochem. Soc.105, 402 (1958)). For deep etching, the macroporous silicon formationmethod in n-type Si appears to be highly desirable (See, e.g., V.Lehman, J. Electrochem. Soc. 143, 385 (1996), and H. Ohji et al.,Sensors and Actuators 82, 254 (2000)). In n-type (100) Si, holes asminority carriers are responsible for etching reaction. In a typicalexperimental configuration, light illumination from the back surfacegenerates holes there which diffuse to the front surface. Since theelectric field is strongest at the pore tip, a majority of holes areconsumed at the tip resulting in near vertical etching of the Si.Therefore, in lightly doped n-type Si, anisotropic etching is primarilyattributed to hole-depletion effect. For p-type Si, the holes arealready in the majority, so no illumination is required. However, inorder to achieve anisotropic vertical etching, surface passivationagents are required. Recent work has demonstrated that profiles similarto n-type Si may be possible in p-type Si as well (See e.g., R, B.Wehrspohn et al., J. Electrochem. Soc. 145, 2958 (1998)).

For either n, or p-type Si, anodic etching is a complex function ofwafer resistivity, crystal orientation, surface preparation, currentdensity, and illumination intensity. For space solar cells, anodic etchprocesses for wafers with resistivities in the range of 10-20 ohm-cmneed to be more extensively developed. FIG. 17 shows two examples ofanodic etching in (100) n-type Si showing vertical trenches with depthsin the 8-13 μm range and widths in the 0.05 to ˜0.3 μm range. Theseresults demonstrate the potential of the anodic etching process as alow-cost, high throughput alternative for slow and expensive DRIEtechniques. Another important consideration, particularly for solar cellapplications, is the absence of plasma-induced surface damage.

3. Characterization of Subwavelength Periodic Microscopic Structures inSilicon

Spectral reflectance measurements provide information about refectionand absorption characteristics of subwavelength random and periodicmicroscopic structures. FIG. 18 shows hemispherical reflectancemeasurements from the random textured Si surface shown in FIG. 11. It isseen that overall reflection has been reduced to ≈1% for wavelengths <1μm, with increasing reflectance at wavelengths >1 μm which representslight transmitted from the wafer and reflected into the detector. Forcomparison, hemispherical reflectance from the planar Si surface is alsoshown.

Generally, for rectangular periodical profiles, narrow, low reflectancespectral bands are observed. For the 0.5-μm period structure shown inFIG. 12 b, FIG. 19 is a graph of the hemispherical spectral reflectancefor electric field parallel (TE) and perpendicular (TM) to the gratinglines. It is seen that TM-reflectance is lower than TE, and resonancereflection minima for two polarizations don't occur at the samewavelengths. For both polarizations, overall reflection is lower thanthe planar surface. Since for a period of 0.5-μm, there are no radiativediffraction orders at wavelengths >0.5 μm, all the light lost inreflection is transmitted into the Si substrate and distributed intovarious diffracted orders. Calculations by the present inventor usingGSOLVER™ predict similar reflectance response for deeply etched gratingmicroscopic structures.

4. Performance of Grating Solar Cells

Grating solar cells, or photodetectors can be made by simply addinglaser interference lithography and RIE/deposition steps to the devicefabrication sequence described hereinabove (See, for example, A. H.Fahrenbruch and R. H. Bube in Fundamentals of Solar Cells, AcademicPress (1983)). FIG. 20 presents preliminary data, but no attempt hasbeen made to optimize junction, contacts and grating profiles. FIG. 20plots one-sun (AM0) light current voltage (LIV) measurements from˜0.25-1.0-μm deep; 0.8-μm period grating solar cells. For comparison,planar surface response is also shown. It is seen that for gratingstructure # 2, short-circuit current (J_(SC)) is increased by ˜1.6mA/cm² in comparison with a planar surface. The current response ofgrating structure # 1 is lower than planar surface. The low,open-circuit voltages (V_(OC)) and fill factors are likely due to thelack of optimum junction formation on grating surfaces (See, e.g.,Saleem H. Zaidi et al., IEEE PVSC 29 (2002)).

FIG. 21 shows AM0 LIV measurements from 10-μm period (grating region #2) and 0.8 μm period (grating region # 1) 2D grating microscopicstructures shown in FIG. 13 d and FIG. 13 f, respectively. It is seenthat the 10 μm period structure has enhanced J_(SC) by ˜9.8 mA/cm² incomparison with the planar surface, whereas the 0.8 μm period responseis only slightly improved. This is likely due to lack of optimumjunction formation on extremely thin microscopic structures. FIG. 22shows AM0 LIV measurements for a 10 μm period 1D (grating region # 2,FIG. 13 a) and an 0.8-μm period (grating region # 1, FIG. 13 c) 1Dgrating structure; for comparison, planar surface response is alsoshown. It is again observed that 10 μm period structure has enhancedJ_(SC) by ˜6.5 mA/cm², whereas the 0.8 μm period structure hassignificantly lower performance. FIG. 23 plots spectral response of 1D(FIG. 23 a, grating region # 2, FIG. 22) and 2D gratings (FIG. 23 b,grating region # 2, FIG. 21) and, for comparison, planar surfaceresponse is plotted. It is seen that spectral response of 1D gratingmicroscopic structures is poor in most of the UV-Visible region. Incomparison with 1D grating structure, 2D hole pattern exhibitssignificantly superior performance. The degradation of short wavelengthresponse may be due to RIE-induced surface damage.

In summary, the grating solar cell data shows that significantperformance gains can be achieved using appropriately designed gratingmicroscopic structures, removal of RIE-induced surface damage, andoptimization of p-n junctions.

a. Removal of RIE Surface Damage:

The spectral response measurements in FIG. 23 illustrate that somephoto-generated carriers are lost to RIE-induced surface damage.RIE-induced surface damage has been extensively investigated. Forexample, S. W. Pang et al. in J. Appl. Phys. 54, 3272 (1983) haveidentified several ways of removing surface damage. More recently, D. S.Ruby et al., 28^(th) IEEE PVSC, 75 (2000) describe removal of RIE damageon randomly textured Si surfaces using a 40% KOH and nitric acid (Nitricacid: hydrofluoric acid: water in 10:1:8 volume ratio) for roomtemperature etch times of ˜60-300 and 10-20 s, respectively. Byincorporation of damage-removal etch (DRE) treatments, textured regionIQEs identical to planar surfaces have been regenerated. FIG. 12 hereofshows the SEM output for as-RIE etched rectangular profiles followingRIE and PECVD oxide deposition cycles. By incorporating KOH, or nitricetch treatments, well-defined grating (FIG. 15) and random microscopicstructures (FIG. 16) can be produced, both of which help confine lightwhile removing the RIE-induced surface damage. This etching proceduretherefore removes sidewall surface damage as well as providingcontrollability for the light interaction due to inverted pyramidstructures.

Another alternative to isotropic Si etching is plasma-less etching suchas a XeF₂-based, low-vacuum etching (See, e.g., D. E. Ibbotson et al.,J. Appl. Phys. 56, 2939 (1984)).

b. Conformal Junction Formation on Deeply Etched Vertical Surfaces:

RIE surface damage can be removed using the wet-chemical DRE treatmentsdiscussed hereinabove. However, due to advantages of dry semiconductorprocessing, it is preferable to remove surface damage without resortingto wet-chemical etching chemistry. Ion implantation has beeninvestigated for junction formation. Ion implantation has been used forjunction formation for solar cells (See for example, E. C. Douglas andR. V. D'aillo, IEEE Trans. Elect. Dev. 27, 792 (1980)). During theimplantation process, the surface is partially amorphized as taught inIon Implantation and Beam Processing, edited by J. S. Williams and J. M.Poate, Academic Press (1984). According to their teachings, the degreeof amorphization is a function of dose level and implant energy. Inorder to repair the damage, annealing at high temperature tore-crystallize the ion-implanted amorphous layers is performed. Thisprocess proceeds epitaxially on the underlying crystalline substrate;for Si this solid phase re-crystallization starts at a temperature of˜525° C. During a constant temperature re-crystallization process, theamorphous-crystalline interface moves towards the surface as a functionof time until the entire amorphous layer is crystallized. Thepossibility that during the implant damage repair process, the RIEsurface damage may also be repaired has been investigated by the presentinventor; random, RIE-textured, nanoscale surfaces shown in FIG. 11 wereused. It is to be noticed that the random features on this surfaceprovide significantly more open area for damage than, for example, aperiodic surface. FIG. 24 shows internal quantum efficiency (IQE)measurements from a solar cell fabricated on such a surface usingconventional gas-source diffusion for junction formation. The ratio ofIQE measurements from RIE-textured and planar regions shows that due tosurface damage, the textured region IQE is suppressed over the entirespectral region. FIG. 25 shows the IQE measurements from solar cellsfabricated on random RIE-textured surfaces using ion implantation. Theratio of IQE measurements from RIE-textured and planar regions showsthat due to the amorphization repair process, both the implant and RIEdamage have been removed, resulting in the textured region IQE beingsignificantly higher than the planar region over most of the spectralregion. FIG. 25 also demonstrates a maximum enhancement of ˜5.4 at λ˜1.1μm, which is greater by a factor of 2 relative to the rectangulargrating case shown in FIG. 11. Therefore, using an implantationtechnique for junction formation, superior grating solar cells can befabricated without any surface damage. Recent developments inplasma-assisted doping techniques show that implants typical of solarcells can be provided by minor modifications of plasma chamberstypically used for reactive ion etching (See, for example, M. J.Goeckner et al., J. Vac. Sci. Technol. B 17, 2290 (1999)).

c. Grating Solar Cells Fabrication Using Gas Source Diffusion:

The process of grating formation using reactive ion etching techniquesintroduces contamination and subsurface plasma-induced damage that isnot completely removed even by a complete RCA clean process. Therefore,fabrication of Si solar cells and other photosensitive devices has to bemodified from the teachings in Fundamentals of Solar Cells, supra. Atypical grating solar cell fabrication procedure in accordance with thepresent invention is as follows using p-type Si having 8-16 Ω-cmresistivity and a thickness of about 300 μm as an example of thestarting material:

a) KOH, or dry etch thinning of active regions to ˜50 μm using a PECVDnitride mask;

b) Fabrication of appropriate front, back, and sidewall grating andrandom microscopic structures using reactive ion and/or anodic etching;

c) Complete RCA cleaning to remove surface contamination;

d) RIE-induced surface damage removal using wet-chemical and dry etchingincluding KOH, nitric acid, and XeF₂ as described in section 4.a,hereof;

e) Formation of n-type (Phosphorous doping) junction using gas sourcedoping, or solid source diffusion in accordance with the teachings ofFundamentals of Solar Cells, supra; and

f) Formation of n and p contacts using metal stacks as taught inFundamentals of Solar Cells, supra.

d. Grating Solar Cells Fabrication Plasma Doping:

Ion implantation for junction formation has been shown to be desirablefor removing RIE-induced surface damage, as described in section 4.b,hereof. Therefore, the grating solar cells and other photosensitivedevices can be formed using the following as a typical sequence usingp-type Si having 8-16 Ω-cm resistivity and thickness of about 300 μm, asan example of the starting material:

a) KOH-thinning of active regions to ˜50 μm using a PECVD nitride mask;

b) Fabrication of appropriate front, back, and sidewall grating andrandom microscopic structures using appropriate reactive ion and/oranodic etching;

c) Complete RCA clean to remove surface contamination;

d) n-type junction formation using plasma implantation; typicalparameters are: ion species ³¹P⁺; energy ˜5 KeV; and Dose ˜2.5×10¹⁵cm⁻²;

e) Furnace implant anneal and passivation oxide growth at ˜1000° C. for30 min in O₂ atmosphere; and

f) Formation of n and p contacts using metal stacks as taught inFundamentals of Solar Cells, supra.

Note that ion implantation can also be achieved using ion implantationtechniques described in section 4.b hereof.

5. Discussion of Grating Solar Cell Results

A detailed design, modeling, fabrication, reflectance and IQEcharacterization of subwavelength Si microscopic structures integratedinto solar cells has been described. By combining RIE etching with PECVDoxide deposition, wafer cleaning, wet-chemical damage removal etches,and ion implanted junctions, undamaged Si surfaces can be recovered.FIG. 26 a shows a diagram of a solar cell where the active region isthinned, 54, while surface protection against breakage is achieved byun-etched regions. SEM output for this embodiment is shown in FIG. 26 bhereof. With appropriate PECVD, or LPCVD nitride masks, a thick wafercan be thinned to about 50-μm while leaving thicker regions to supportthe thin film. Alternatively, one can also use XeF₂ etching for waferthinning. In accordance with the present invention, the use of thin Sifilms for solar cells in the space environment has significantadvantages. For example, reduced weight, which lowers the launch costs,and enhanced radiation tolerance. In earlier work on thin-filmcrystalline Si solar cells, significant radiation-tolerance could not beachieved due to incomplete optical confinement and the inability tocollect deeply generated electron-hole pairs. Several subwavelengthoptical structures etched almost entirely throughout the thin film thatserve the dual purpose of helping to increase optical absorption andreducing carrier recombination losses are described herein.Subwavelength optical microscopic structures increase absorption oflight by the thin film by enhanced scattering and waveguide mechanisms.The presence of high-quality three-dimensional junctions throughout thethin film separated by distances between 1 and 10 μm range help collecta majority of electron-hole pairs before losing them to recombination.

The foregoing description of the invention has been presented forpurposes of illustration and description and is not intended to beexhaustive or to limit the invention to the precise form disclosed, andobviously many modifications and variations are possible in light of theabove teaching.

The embodiments were chosen and described in order to best explain theprinciples of the invention and its practical application to therebyenable others skilled in the art to best utilize the invention invarious embodiments and with various modifications as are suited to theparticular use contemplated. It is intended that the scope of theinvention be defined by the claims appended hereto.

1. A method for forming thin film solar cells and photodetectors havingincreased light absorption and radiation tolerance, which comprises thesteps of: (a) forming a plurality of macroscopic features having achosen periodic spacing, width and depth on a first surface of a dopedfilm suitable for solar cell or photodetector applications and formedtherefrom, each feature having at least one surface perpendicular to thefirst surface of the film and one surface parallel thereto, there alsobeing formed surfaces between each of the plurality of macroscopicfeatures (b) attaching an electrical contact to at least a portion of asecond surface of the film, the second surface being generally parallelto and spaced apart a chosen thickness from the first surface; (c)doping the region of the surfaces of the plurality of macroscopicfeatures and the region of the surfaces between each of the plurality ofmacroscopic features, forming thereby a p-n junction with the dopedfilm; (d) attaching an electrical contact to at least a portion of thejunction, whereby the film is adapted to produce a photovoltaic responseto light having a chosen wavelength or wavelengths incident thereon, theperiod of the macroscopic features, the width and the depth thereof andthe thickness between the first and second surfaces of the film beingchosen such that minority carrier diffusion length for carriers producedby the photovoltaic response of the film is larger than the largestdistance between a location interior to the film and the junction; and(e) randomly etching 3-dimensional microscopic structures havingdimensions less than the wavelength or wavelengths of light onto thesurfaces of the macroscopic features which are parallel to the surfaceof the film and onto the surfaces between each of the plurality ofmacroscopic features such that light incident thereon is scattered intoa multiplicity of high diffraction orders which propagate obliquely tothe direction of incidence of the light, thereby trapping the incidentlight by total internal reflection and increasing light absorption bythe film.
 2. The method as described in claim 1, wherein the thin filmhas a thickness between 10 μm and 50 μm.
 3. The method as described inclaim 1, further comprising the step of etching random, 3-dimensionalmicroscopic structures having dimensions smaller than the wavelength orwavelengths of light onto the second surface of the film.
 4. The methodas described in claim 1, further comprising the step of etching random,3-dimensional microscopic structures having dimensions smaller than thewavelength or wavelengths of light onto the surfaces of the plurality ofmacroscopic features perpendicular to the first surface of the film. 5.The method as described in claim 1, further comprising the step ofgenerating a pyramidal pattern having a period approximately equal tothe period of the plurality of macroscopic features onto the surfaces ofthe plurality of macroscopic features perpendicular to the first surfaceof the film.
 6. The method as described in claim 1, further comprisingthe step of generating a microscopic grating structure having a secondchosen period onto the surfaces of the plurality of macroscopic featuresperpendicular to the first surface of the film wherein the second chosenperiod is smaller than the chosen period of the macroscopic features,whereby incident light thereon is distributed into higher diffractionorders which are trapped within the macroscopic features.
 7. The methodas described in claim 6, further comprising the step of generating amicroscopic grating structure having a third chosen period onto thesecond surface of the film wherein the third chosen period is smallerthan the chosen period of the macroscopic features, whereby incidentlight thereon is distributed into higher diffraction orders which aretrapped within the film.
 8. The method as described in claim 1, whereinthe plurality of macroscopic features is a 2-dimensional structure. 9.The method as described in claim 1, wherein the doped film suitable forsolar cell and photodetector applications is selected from the groupconsisting of silicon and gallium arsenide.
 10. The method as describedin claim 9, wherein the silicon comprises p-doped silicon and thejunction is an n on p junction.
 11. The method as described in claim 9,wherein the silicon comprises n-doped silicon and the junction is a p onn junction.
 12. The method as described in claim 1, wherein said step ofdoping the surfaces of the plurality of macroscopic features and thesurfaces between each of the plurality of macroscopic features isachieved using a method selected from the group consisting of gas sourcediffusion, solid source diffusion, ion implantation, and plasma doping.13. The method as described in claims 1, 3, or 4, wherein said step ofrandomly etching 3-dimensional microscopic structures is performed usinga method selected from the group consisting of reactive ion etching,anodic etching, and wet-chemical etching.
 14. The method as described inclaim 13, further comprising the step of removing surface damageresulting from said step of random reactive ion etching of 3-dimensionalmacroscopic features and microscopic structures by selective etching thesurface using materials selected from the group consisting of NaOH, KOH,nitric acid, and XeF₂.
 15. The method as described in claims 1, 5, 6 or7, wherein said step of forming a plurality of macroscopic featureshaving a chosen periodic spacing, width and depth, said step ofgenerating a microscopic grating structure, and said step of generatinga pyramidal pattern are performed using a method selected from the groupconsisting of reactive ion etching, wet-chemical etching, and anodicetching.
 16. The method as described in claim 15, further comprising thestep of removing surface damage resulting from said step of random,reactive ion etching of 3-dimensional macroscopic and microscopicstructures by selective etching the surface using materials selectedfrom the group consisting of NaOH, KOH, nitric acid, and XeF₂.
 17. Amethod for forming solar cells and photodetectors having increased lightabsorption and radiation tolerance, which comprises the steps of: (a)forming a plurality of macroscopic features having a chosen periodicspacing, a chosen width and a chosen depth on a first surface of a dopedfilm suitable for solar cell and photodetector applications and formedtherefrom, each feature having at least one surface perpendicular to thefirst surface of the film and one surface parallel thereto, there alsobeing formed surfaces between each of the plurality of macroscopicfeatures; (b) attaching an electrical contact to at least a portion of asecond surface of the film, the second surface being generally parallelto and spaced apart a chosen thickness from the first surface; (c)doping the region of the surfaces of the plurality of macroscopicfeatures and the region of the surfaces between each of the plurality ofmacroscopic features, thereby forming a p-n junction with the dopedfilm; (d) attaching an electrical contact to at least a portion of thedoped surfaces, whereby the film is adapted to produce a photovoltaicresponse to light having a chosen wavelength or wavelengths incidentthereon, the period of the macroscopic features, the width and the depththereof, and the thickness between the first and second surfaces of thewafer being chosen such that minority carrier diffusion length forcarriers produced by the photovoltaic response of the film is largerthan the largest distance between a location interior to the film andthe junction; and (e) generating a microscopic grating structure havinga second chosen period on the surface of each feature parallel to thefirst surface of the film wherein the second chosen period is smallerthan the chosen period of the macroscopic features, whereby incidentlight thereon is distributed into higher diffraction orders which aretrapped within the macroscopic features.
 18. The method as described inclaim 17, wherein the thin film has a thickness between 10 μm and 50 μm.19. The method as described in claim 17, further comprising the step ofetching random, 3-dimensional microscopic structures having dimensionssmaller than the wavelength or wavelengths of light onto the secondsurface of the film.
 20. The method as described in claim 17, whereinthe doped film suitable for solar cell and photodetector applications isselected from the group consisting of silicon and gallium arsenide. 21.The method as described in claim 20, wherein the silicon comprisesp-doped silicon and the junction is an n on p junction.
 22. The methodas described in claim 20, wherein the silicon comprises n-doped siliconand the junction is a p on n junction.
 23. The method as described inclaim 17, wherein said step of doping the surfaces of the plurality ofmacroscopic features and the surfaces between each of the plurality ofmacroscopic features is achieved using a method selected from the groupconsisting of gas source diffusion, solid source diffusion, ionimplantation, and plasma doping.
 24. The method as described in claim19, wherein said step of randomly etching 3-dimensional microscopicstructures is performed using a method selected from the groupconsisting of reactive ion etching, anodic etching, and wet-chemicaletching.
 25. The method as described in claim 24, further comprising thestep of removing surface damage resulting from said step of randomreactive ion etching of 3-dimensional macroscopic features andmicroscopic structures by selective etching the surface using materialsselected from the group consisting of NaOH, KOH, nitric acid, and XeF₂.26. The method as described in claim 14, further comprising the step ofgenerating a grating structure having a third chosen period onto thesecond surface of the film wherein the third chosen period is smallerthan the chosen period of the macroscopic features, whereby incidentlight thereon is distributed into higher diffraction orders which aretrapped within the silicon film.
 27. The method as described in claim14, further comprising the step of generating a microscopic gratingstructure having a fourth chosen period onto the surfaces of theplurality of macroscopic features perpendicular to the surface of thefilm wherein the fourth chosen period is smaller than the chosen periodof the macroscopic features, whereby incident light thereon isdistributed into higher diffraction orders which are trapped within themacroscopic features.
 28. The method as described in claims 17, 26 or27, wherein said step of forming a plurality of macroscopic featureshaving a chosen periodic spacing, width and depth, and said step ofgenerating a grating structure, are performed using a method selectedfrom the group consisting of reactive ion etching, anodic etching, andwet-chemical etching.
 29. The method as described in claim 28, furthercomprising the step of removing surface damage resulting from said stepof random reactive ion etching of 3-dimensional macroscopic features andmicroscopic structures by selective etching the surface using materialsselected from the group consisting of NaOH, KOH, nitric acid and XeF₂.30. A method for forming solar cells and photodetectors having increasedlight absorption and radiation tolerance, which comprises the steps of:(a) forming a microscopic grating structure having a chosen period andchosen depth on a first surface of a doped film suitable for solar celland photodetector applications; (b) attaching an electrical contact onat least a portion of a second surface of the film, the second surfacebeing generally parallel to and spaced apart a chosen thickness from thefirst surface, wherein the chosen depth of the microscopic gratingstructure is less than the chosen thickness of the film; (c) doping thesurfaces of the generated grating structure, forming thereby a p-njunction with the film; and (d) attaching an electrical contact to atleast a portion of the doped surfaces of the generated microscopicgrating structure, whereby the film is adapted to produce a photovoltaicresponse to light having a chosen wavelength or wavelengths incidentthereon, the chosen period of the microscopic grating structure and thethickness between the first and second surfaces of the film being chosensuch that minority carrier diffusion length for carriers produced by thephotovoltaic response of the film is larger than the largest distancebetween a location interior to the film and the junction.
 31. The methodas described in claim 1, wherein the thin film has a thickness between10 μm and 50 μm.
 32. The method as described in claim 30, furthercomprising the step of etching random, 3-dimensional microscopicstructures having dimensions smaller than the wavelength or wavelengthsof light onto the second surface of the film.
 33. The method asdescribed in claim 30, wherein the doped film suitable for solar celland photodetector applications is selected from the group consisting ofsilicon and gallium arsenide.
 34. The method as described in claim 33,wherein the silicon comprises p-doped silicon and the junction is an non p junction.
 35. The method as described in claim 33, wherein thesilicon comprises n-doped silicon and the junction is a p on n junction.36. The method as described in claim 30, wherein, the chosen depth ofthe microscopic grating structure on the first surface is comparable tothe chosen thickness of the film.
 37. The method as described in claim30, wherein the microscopic grating structure on the first surfacecomprises a 2-dimensional structure.
 38. The method as described inclaim 30, wherein said step of doping the surfaces of the plurality ofmacroscopic features and the surfaces between each of the plurality ofmacroscopic features is achieved using a method selected from the groupconsisting of gas source diffusion, solid source diffusion, ionimplantation, and plasma doping.
 39. The method as described in claim32, wherein said step of randomly etching 3-dimensional microscopicstructures is performed using a method selected from the groupconsisting of reactive ion etching, anodic etching, and wet-chemicaletching.
 40. The method as described in claim 39, further comprising thestep of removing surface damage resulting from said step of randomreactive ion etching of 3-dimensional microscopic structures byselective etching the surface using materials selected from the groupconsisting of NaOH, KOH, nitric acid and XeF₂.
 41. The method asdescribed in claim 30, wherein said step of forming a microscopicgrating structure, is performed using a method selected from the groupconsisting of reactive ion etching, wet-chemical etching, and anodicetching.
 42. The method as described in claim 41, further comprising thestep of removing surface damage, resulting from said step of fabricatingmicroscopic grating structures by reactive ion etching, by usingmaterials selected from the group consisting of NaOH, KOH, XeF₂, andnitric acid.
 43. A photovoltaic device having increased light absorptionand radiation tolerance, which comprises in combination: (a) a dopedfilm suitable for photovoltaic applications; (b) a plurality ofmacroscopic features having a chosen periodic spacing, a chosen widthand a chosen depth formed on a first surface of said film, eachmacroscopic feature having at least one surface perpendicular to thefirst surface of said film and one surface parallel thereto, there alsobeing formed surfaces between each of said plurality of macroscopicfeatures, and the region of the surfaces of said plurality ofmacroscopic features and the region of the surfaces between each of saidplurality of macroscopic features being doped, forming thereby a p-njunction with said film; (c) an electrical contact attached to at leasta portion of a second surface of said film, the second surface beinggenerally parallel to and spaced apart a chosen thickness from the firstsurface thereof; (d) an electrical contact attached to at least aportion of said junction, whereby said film is adapted to produce aphotovoltaic response to light having a chosen wavelength or wavelengthsincident thereon, the period of the macroscopic features, the width andthe depth thereof, and the thickness between the first and secondsurfaces of said film being chosen such that minority carrier diffusionlength for carriers produced by the photovoltaic response of the film islarger than the largest distance between said junction and a locationwithin said film; and (e) a randomly etched 3-dimensional microscopicstructure having dimensions less than the wavelength or wavelengths oflight disposed on the surfaces of the macroscopic features which areparallel to the surface of said film and on the surfaces between each ofthe plurality of macroscopic features such that light incident thereonis scattered into a multiplicity of high diffraction orders whichpropagate obliquely to the direction of incidence of the light, therebytrapping the incident light by total internal reflection and increasinglight absorption by said film.
 44. The photovoltaic device as describedin claim 43, wherein the thin film has a thickness between 10 μm and 50μm, and said plurality of macroscopic features each have a chosen widthbetween 1 μm and 50 μm, a depth of between 10 μm and 30 μm, and aspacing of between 0.5 μm and 5 μm.
 45. The photovoltaic device asdescribed in claim 43, further comprising a random, 3-dimensionalmicroscopic structure having dimensions smaller than the wavelength orwavelengths of light etched onto the second surface of said film. 46.The photovoltaic device as described in claim 43, further comprisingrandom, 3-dimensional microscopic structures having dimensions smallerthan the wavelength or wavelengths of light etched onto the surfaces ofsaid plurality of macroscopic features perpendicular to the surface ofsaid film.
 47. The photovoltaic device as described in claim 43, furthercomprising a pyramidal pattern having a period approximately equal tothe period of said plurality of macroscopic features etched onto thesurfaces of said plurality of macroscopic features perpendicular to thesurface of said film.
 48. The photovoltaic device as described in claim43, further comprising a microscopic grating structure having a secondchosen period formed onto the surfaces of said plurality of macroscopicfeatures perpendicular to the surface of said film wherein the secondchosen period is smaller than the chosen period of said macroscopicfeatures, whereby incident light thereon is distributed into higherdiffraction orders which are trapped within said macroscopic features.49. The photovoltaic device as described in claim 43, further comprisinga microscopic grating structure having a third chosen period formed ontothe second surface of said film wherein the third chosen period issmaller than the chosen period of the macroscopic features, wherebyincident light thereon is distributed into higher diffraction orderswhich are trapped within the film.
 50. The photovoltaic device asdescribed in claim 43, wherein said plurality of macroscopic featurescomprises a 2-dimensional structure.
 51. The photovoltaic device asdescribed in claim 43, wherein said plurality of microscopic gratingstructures is a 2-dimensional structure.
 52. The photovoltaic device asdescribed in claim 42, wherein said doped film suitable for photovoltaicapplications is selected from the group consisting of silicon andgallium arsenide.
 53. The photovoltaic device as described in claim 50,wherein the silicon comprises p-doped silicon and the junction is an non p junction.
 54. The photovoltaic device as described in claim 50,wherein the silicon comprises n-doped silicon and the junction is a p onn junction.
 55. A photovoltaic device having increased light absorptionand radiation tolerance, which comprises in combination: (a) a dopedfilm suitable for photovoltaic applications; (b) a plurality of siliconmacroscopic features having a chosen periodic spacing, a chosen widthand a chosen depth formed on a first surface of said film, each featurehaving at least one surface perpendicular to the first surface of saidfilm and one surface parallel thereto, there also being formed surfacesbetween each of said plurality of macroscopic features; (c) anelectrical contact attached to at least a portion of a second surface ofsaid film, the second surface being generally parallel to and spacedapart a chosen thickness from the first surface, and the region of thesurfaces of said plurality of macroscopic features and the region of thesurfaces between each of said plurality of macroscopic features beingdoped, forming thereby a p-n junction with said film; (d) an electricalcontact attached to at least a portion of said junction, whereby saidfilm is adapted to produce a photovoltaic response to light having achosen wavelength or wavelengths incident thereon, the period of saidmacroscopic features, the width and the depth thereof and the thicknessbetween the first and second surfaces of said film being chosen suchthat minority carrier diffusion length for carriers produced by thephotovoltaic response of said film is larger than the largest distancebetween a location interior to said film and said junction; and (e) amicroscopic grating structure having a second chosen period formed onthe surface of each of said macroscopic features parallel to the firstsurface of said film wherein the second chosen period is smaller thanthe chosen period of said macroscopic features, whereby incident lightthereon is distributed into higher diffraction orders which are trappedwithin said macroscopic features.
 56. The photovoltaic device asdescribed in claim 53, wherein the thin film has a thickness between 10μm and 50 μm, and said plurality of macroscopic features each have achosen width between 1 μm and 50 μm, a depth of between 10 μm and 30 μm,and a spacing of between 0.5 μm and 5 μm.
 57. The photovoltaic device asdescribed in claim 55, further comprising a random, 3-dimensionalmicroscopic structure having dimensions smaller than the wavelength orwavelengths of light formed the second surface of said film.
 58. Thephotovoltaic device as described in claim 55, wherein said doped filmsuitable for photovoltaic applications is selected from the groupconsisting of silicon and gallium arsenide.
 59. The photovoltaic deviceas described in claim 58, wherein the silicon comprises p-doped siliconand the junction is an n on p junction.
 60. The photovoltaic device asdescribed in claim 58, wherein the silicon comprises n-doped silicon andthe junction is a p on n junction.
 61. The photovoltaic device asdescribed in claim 55, further comprising a microscopic gratingstructure having a third chosen period formed onto the second surface ofsaid film wherein the third chosen period is smaller than the chosenperiod of said macroscopic features, whereby incident light thereon isdistributed into higher diffraction orders which are trapped within saidfilm.
 62. The photovoltaic device as described in claim 55, furthercomprising a microscopic grating structure having a fourth chosen periodformed onto the surfaces of the plurality of macroscopic featuresperpendicular to the surface of said film wherein the fourth chosenperiod is smaller than the chosen period of said macroscopic features,whereby incident light thereon is distributed into higher diffractionorders which are trapped within said macroscopic features.
 63. Aphotovoltaic device having increased light absorption and radiationtolerance, which comprises in combination: (a) a doped film suitable forphotovoltaic applications; (b) a microscopic grating structure having achosen period, a chosen width and chosen depth formed on a first surfacesaid film, the surfaces of said grating structure being doped, formingthereby a p-n junction with said film; (c) an electrical contactattached to at least a portion of a second surface of said film, thesecond surface being generally parallel to and spaced apart a chosenthickness from the first surface, wherein the chosen depth of saidmicroscopic grating structure is equal to the chosen thickness of saidfilm; and (d) an electrical contact attached to at least a portion ofthe doped surfaces of said grating structure, whereby said film isadapted to produce a photovoltaic response to light having a chosenwavelength or wavelengths incident thereon, the chosen period of saidmicroscopic grating structure and the thickness between the first andsecond surfaces of said film being chosen such that minority carrierdiffusion length for carriers produced by the photovoltaic response ofsaid film is larger than the largest distance between a locationinterior to said film and said junction.
 64. The photovoltaic device asdescribed in claim 63, wherein the thin film has a thickness between 10μm and 50 μm.
 65. The photovoltaic device as described in claim 63,wherein the chosen depth of said microscopic grating structure on thefirst surface is less than the chosen thickness of said film.
 66. Thephotovoltaic device as described in claim 65, further comprising arandom, 3-dimensional microscopic structure having dimensions smallerthan the wavelength or wavelengths of light formed onto the secondsurface of said film.
 67. The photovoltaic device as described in claim63, wherein said doped film suitable for photovoltaic applications isselected from the group consisting of silicon and gallium arsenide. 68.The photovoltaic device as described in claim 67, wherein the siliconcomprises p-doped silicon and the junction is an n on p junction. 69.The photovoltaic device as described in claim 67, wherein the siliconcomprises n-doped silicon and the junction is a p on n junction.
 70. Thephotovoltaic device as described in claim 63, wherein said microscopicgrating structure comprises a 2-dimensional structure.